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By R. R. Boucher, O. J. C. Runnalls

A pronounced thermal effect has been observed on heating or cooling a1wninum-rich Al-U and Al-Pu alloys. From microscopic and X-ray diffractionstudies, the effectl has been attributed to trnsfor)nations in the inlemetallic phases UAl, and PuAl , involuing rearrangement or cluslering of vacancies The transformation obsrved in Al-20 wi oct U alloys occurred near the a Al-UAl4 eutectic tem-perature of 646°C making it difjicult to detect from heating curves. When cooling, howeoer, thermal mad X-ray analyses indicnted that the high-temperati~re phase labeled p UAL, precipitated initially during euitectic solidification. As solidification continued and after an induction period o-f 5 lo 20 tnin the nu-cleatiorz and growth of the low- twmperature phase, a UAl4 produced an euolution of energy which raised the observed alloy temperature by 1° to 2°C. in Al-Pu alloys the transformation occurred at 645°C, 5 deg below the eutectic solidification temperccture. The eslimated latent heat of transformation was 25 +5 cnl per g PuAl,. The high-tetnpevcl-ture forms of UAl, and PuAl, were easily 9-etccined by chill casting Al-U and Al-Pu alloys and on reheating the alloys the trcltzsforrnation to the a phase was sluggish even above 600°C. Separated single cryslals o-f UAl4, joy example, showed no evidence Of transformalion after heating for 16 hr at 620°C. The transformation rates increased yapidly enough with increasing temperature, however, that a a spontaneous liberation of energy lens observed on occasion when bealing cast Al-20 wt pet U to neal- the RECENT phase studies on A1-Pu alloys have indicated that earlier reported equilibrium diagrams should be modified to take account of several poly- morphic transformations in the intermetallic compound PuAl,.' During the course of the latter work an unexpected heat evolution was observed while cooling a solid alloy consisting of a mixture of a aluminum and PuA1,. The evolution occurred at 645°C, y below the a A1-Pu A1, eutectic solidification temperature. Subsequent thermal-analysis experiments with A1-U alloys showed that heat was evolved there also at a temperature nearly coincident with the a A1-UA1, eutectic solidification temperature of 646°. A search of the literature revealed that similar thermal effects had been observed before for both A1-U and A1-Pu but had never been fully explained.2,3 The purpose of the present paper is to describe thermal-analysis and X-ray diffraction experiments which have led to the conclusion that the thermal effects are due to transformations which involve the rearrangement of vacancies in the intermetallic compounds UA1, and PuA1,. EXPERIMENTAL PROCEDURE The A1-U alloys were prepared by heating super-pure aluminum (99.99 pct +) obtained from the Aluminum Co. of Canada in a graphite crucible surrounded by an induction coil. At 1000°C high-purity uranium metal produced by the Eldorado Mining and Refining Co., Ltd. was dropped into the liquid aluminum and was dissolved completely within 15 min. The impurities in the uranium were A1—4 ppm, Ca-4, C-70, Cr-3, Cu-6, Fe-30, Mg-2, Mn-10, Ni-25, Si-25, and Zn-2. The A1-Pu alloys were prepared by reacting plutonium dioxide with liquid aluminum under cryolite (3 NaF . AlF,) for 10 min at 1100°C in graphite crucibles exposed to the air. The plutonium was 99.8 pct pure, containing trace impurities of Ca, Cu, Fe, Pb, Si, and Zn. The liquid alloys were usually poured into water-cooled molds to provide castings of uniform composition from which samples could be cut for heat treatment and thermal-analysis experiments.

Jan 1, 1965

By L. Moyd, P. Moyd

The first commercially available portable gamma ray-neutron beryllium detector, the Rerylometer, was developed by the same group that developed the first practical portable scintillation counter, the Scintillo-meter. This group includes Professor George Brownell, of the Geology Department of the University of Manitoba in winnipeg, and his associates, K. I. Roulston, R. w. Pringle, and R. L. Funt, of the Physics and Engineering Departments of the University of Manitoba. A prototype model was tested in the field by Dr. Brownell during the summer of 1958. Commercial production was undertaken shortly thereafter by Nuclear Enterprises Ltd., of Winnipeg, and a license for manufacture and distribution in the U.S. was granted to Isotopes Specialties Co., of Burbank, California, a division of Nuclear Corporation of America. Early in 1959, we were retained by the 'Mining Division of Minerva Oil Co. to Legin a search throughout North America for minable deposits of beryllium, and to train members of their permanent staff to continue the program. The project included literature sur-veys, interviews with members of various federal, state, and provincial agencies, scanning of our own collection of suites of specimens from various mineral occurrences, and the examination of deposits in the field. The value of a beryllium detector to this program was obvious and arrangements were made to procure one as soon as possible, which resulted in our obtaining and using the first instrument that was produced commercially in the U. S. In addition to the commercially available Berylometer, Mr. William Vaughan and his associates, of the U. S. Geological Survey Geophysics Division, in Denver, have developed and tested several experimental instruments based on the same principles. DETECTOR Principles The detection of beryllium is based on the fact that "hard" gamma rays (1.6 MEV and geater), such as those produced by Antimony convert ordinary beryllium (Be9) to Be8 , with the release of a neutron. The neutrons are counted by a scintillator designed to favor neutron responses while suppressing those of gamma rays. 'The instrument is completely selective for beryllium. No other element can interfere. Instrunlentation The Rerylometer itself, which is cylindrical, is about 8 inches in diameter, 13 inches high, and weighs about 11 pounds. (Figs. 1, 2). The principal components include: 1. A disc of wax to moderate (or "thermalize") neutrons. 2. A boron-enriched polyester-zinc-sulphide fluorescent screen. This material produces strong flashes when struck by thermalized neutrons but only weak flashes from gamma rays. 3. A photomultiplier tube. 4. An electronic circuit, complete with one srnall 71/2-volt dry battery. The photomultiplier tube and electronic circuit convert neutron flashes to electrical impulses, but gamma ray effects are almost

Jan 1, 1961

By Richard Miller

RECENT studies of creep have made it apparent that plastic deforma-tion may occur in metals under stresses less than the elastic limit as deter-mined from short-time tests. In summarizing conclusions drawn from creep tests by various investigators, Tapsell1 said: "It is evident that if a material has a true elastic range, the elastic limit must represent the maximum stress for no creep." The presence of a. definite elastic limit, represented in single crystals by a critical or threshold shearing stress, is claimed by Schmid2, Elam3 and others who have investigated the plastic deformation of single crystals. However, this "law of critical shearing stress" was deter-mined2 from short-time tests, and the measurement of the deformation was made with apparatus primarily designed to observe large amounts of plastic deformation, not to detect elastic changes. Experimental data recently obtained with highly sensitive instru-ments by A. W. Hanson4 on zinc and by Podaschowsky5 on rock salt indicate that the elastic range in single crystals is considerably narrower than formerly was supposed. Moreover, a theoretical possibility of permanent deformation, under the influence of even the smallest shear stress in single crystals above a certain temperature (Td), has been developed by G. I. Taylor6. This evidence seemed to warrant an examination of the elastic limit in large single crystals by means of creep tests. The first metal chosen for examination was zinc.

Jan 1, 1936

By Ray Schmidt

When your committee approached me for a talk on "Mechanics of Secondary Metals Collection," I replied that this subject would probably not be very interesting to a group of engineers and requested permission to dwell on the Westinghouse Salvage Setup. I will attempt to avoid duplicating the points covered by Mr. Bliven. The Westinghouse Electric and Manufacturing Co. has main manufacturing Divisions in 25 cities and 9 different states, scattered throughout the country, as well as Naval Ordnance Plants in two midwest cities, and a Merchant Marine Turbine Plant, and two special War Production Plants in Eastern cities. You can, therefore, see that we must have a well rounded pro- gram with the entire respect and sponsorship of the various Division Managements. That was not so easy to get. Management has been a great deal like the general public in the past. I am sure most of you can remember the not very ancient day when each town had a ragman who had a horse and wagon and went through the streets of the town, from door to door, picking up what scrap he could accumulate. He was known as a junk man, and indeed, with the exception of the very last few years, the attitude of manufacturing management was: "We have a job to do. We have a product to manufacture. We don't have time to bother with the junk business."

Jan 1, 1943

By B. Yarar

Samples of coal from an adit in the Fording River District of British Columbia showed hydrophilic properties between depths of 0-24.5 m (0-80 ft) and was naturally hydrophobic at greater depths. Laboratory experiments indicated that weathered samples (i.e., those mined at 0-24.5 m) could be upgraded by froth flotation at pH32 following slimes removal. The i.e.p. of samples varied regularly between pH = 1.6-4.1, the weathered fractions being at the lower end of the pH scale. These values followed a pattern comparable with the flotation behavior of samples. A patchwise structure for coal surfaces determining the resultant disjoining pressure which in turn determines flotation-non-flotation relationships is postulated.

Jan 1, 1983

By Lane Mitchell

A ceramic product or processed material is a solid composed of materials which have been subjected to heat above 875°F. The raw materials, which are blended together (or in some cases used singly), are selected and utilized for various reasons such as ease of fabrication, aid to processing, to yield desired properties after processing, lack or controllable degree of toxicity or hazard, availability, cost, and perhaps other considerations. Almost all solid inorganic, some organic, and some liquid and gaseous materials have the potential to be used individually in some ceramic product. There are several fundamental functions to be fulfilled in every ceramic product and a number of secondary functions are desirable in specified products. These functions are generally met by the most widely occurring minerals and rocks of the earth and their debris. This fact characterizes ceramics as a field utilizing the raw materials most available to man. Of course, specified products utilize synthetics, organics, and rare inorganics to produce desired results. Any solid nonmetallic product processed by subjection to temperature above a red heat may be called a ceramic product. Widely used construction materials and units, domestic utensils and units, industrial parts to facilitate manufacture, technical components, and aesthetic creations are very often of a ceramic nature because of the durability, inertness, hardness, ease of fabrication, cost, and availability of the ingredients. Often, organics or metals cannot meet desired specifications for some of these products. The rocks and minerals and mineral debris of the earth are largely siliceous. Oxygen and silicon comprise roughly 75% of the earth's crust with aluminum, iron, calcium, and the alkalies following in abundance. Silica ( SiO, ) and silicates can be melted to form glasses. Alumina (A1,0,), present in a mineral com- pound, gives greater durability, hardness, and strength, but lessens the glass-forming property. Iron, calcium, and the other alkalies flux silica and reduce melting points. Thus, sand, which is generally almost pure SiO,, and clay, which is generally hydrated alumina silicate, are the most widely used of all ceramic raw materials-principally because of the glass-forming propensities of silicates. In ceramic formulations, clay is generally a refractory filler or skeletal material, having in the raw state a plasticity derived from its colloidal grain size and its water-loving nature. On the other hand, silica sand is a glass former or nonplastic filler. Clay and silica sand in pure forms are quite refractory, i.e., not easily melted. Clay, although siliceous, is less of a glass former than pure silica and is more refractory. Natural contaminants, such as iron oxide or limestone, adulterate many clays and some sands. These contaminants act as fluxes and reduce the fusion points of the mineral or blends. Glass is made from silica sand by fluxing the sand with strong bases, usually soda ash and limestone. Red building bricks are hard and durable because the sand and clay have been partially fused with help of natural iron oxide serving as a flux. The iron oxide per- forms a dual function, serving as a pigment as well as a flux. In a blend of clay and sand and iron oxide, the sand is more susceptible to fusion than is the clay. Although silica sand and clay are the most widely used raw materials in most ceramic products, many other minerals, and some non- minerals are utilized in products where these materials can produce or aid in achieving desired results. Limestone and dolomite, feldspars, pigmentary minerals, refractory oxides or carbides, and special property producers can

Jan 1, 1975

LIST OF THE MEETINGS OF THE INSTITUTE AND THEIR LOCALITIES FROM ITS ORGANIZATION Transactions Number Place Date Vol Page 1 Wilkes-Barre, Pa May, 1871 1 3 2 Bethlehem, Pa August, 1871 1 10 3 Troy, N Y November, 1871 1 13 4 Philadelphia, Pa February, 1872 1 17 5 New York, N Y May, 1872 1 20 6 Pittsburg, Pa October, 1872 1 25 7 Boston, Mass February, 1873 1 28 8 Philadelphia, Pa May, 1873 2 3 9 Easton, Pa October, 1873 2 7 10 New York, N Y February, 1874 211 11 St Louis, Mo May, 1874 3 3 12 Hazleton, Pa October, 1874 3 8 13 New Haven, Conn February, 1875 3 15 14 Dover, N J May, 1875 4 3 15 Cleveland, 0 October, 1875 4 9 16 Washington, D C February, 1876 4 18 17 Philadelphia, Pat June, 1876, 5 3 18 Philadelphia, Pa October, 1876 5 9 19 New York, N Y February, 1877 5 27 20 Wilkes-Barre, Pa May, 1877 6 3 21 Amenia, N Y October, 1877 6 10

Jan 1, 1917

By Frederick Laist

F. N. FLYNN, Clifton, Ariz.-I would like to ask Mr. Mathewson what percentage of his leaching liquor is wasted at this time? It has a bearing on the question in connection with the New Cornelia, and I think it is a very important question. E. P. MATHEWSON, Anaconda, Mont.-I am not sure what the percentage is now, but we don't discard the strong liquors. Something like 25 per cent. of the wash water taken out each day is sent over a special set of scrap iron tanks, and the copper recovered there. We had a little trouble at first. We did not proceed to use the sponge iron for the reason that the plant we originally contemplated was abandoned for flotation. Our original idea was to use a leaching process on all the tailings of the mill, but we found it would take a great deal of time to build a plant; and the cost of operating the plant we estimated to be about the same and the recovery the same. It was a question of time with us, and we decided to adopt flotation. That changed our plans. We now have the leaching plant, treating the tailings of the old dump, and the flotation applied to the current tailings. The sponge iron was figured for the large plant. We can get all the scrap iron necessary for the small plant-plenty from the scrap produced in the main plant of the smelter.

Jan 12, 1916

By K. G. Black, B. P. Faulkner

Laboratory batch flotation rests are used for comparison of the floatability of ores and for comparison of the effect of various treatments on ore floatability. Although it is difficult to predict exact recoveries for continuous flotation on the basis of batch tests, considerable quantitative information can be obtained through their use. A simple method is presented which provides a convenient means of quantitatively evaluating results from laboratory batch tests. The information obtained is in the form of a discrete flotation rate distribution, which, if desired, can be used directly in a simulation of continuous flotation. Equation of Batch Flotation The validity for batch flotation of the first-order kinetic equation is accepted: [ ] where k is flotation rate of a class of articles and W (t) is weight of particles of the class in cell at time t. Thus, at time t, the fraction of the original amount of the class of particles still remaining in the cell is [ ] where W (0) is weight of class of particles in cell at time zero. If there are several classes of particles in the cell, each with its own flotation rate, k4, the fraction of the particles remaining is [ ] where W (t) is now the total weight of n classes, a, being the original fraction of W (0) belonging to the ith class. Accordingly, [ ] [Fig. 1] shows the result of a typical batch test. Such result can be characterized by a set of particle classes, each set described by a flotation rate, [ki,] and a corresponding fractional magnitude, [ai.] [ ] Multiple Regression Equation Eqs. 3 and 4 may be combined to give

Jan 1, 1973

By F. E. Bash

PREVIOUS to the war, this country depended on Europe for its supply of a number of alloys of great importance in the manufacture of electrical apparatus and equipment. When this source was cut off shortly after the beginning of hostilities and the small stocks in the United States were exhausted, either inferior substitutes had to be used or the manufacture of the apparatus suspended. Since electrical equipment was of primary importance in the prosecution of the war, the substitutes had to be used until the composition and processes of manufacture of the alloys could be determined. Included among these alloys was one generally known as manganin, which is composed chiefly of copper and manganese and which, beside having a low-temperature coefficient of resistance, has a low thermal electromotive force against copper. These qualities make it valuable for the manufacture of electrical instruments and machines in which it is used in the shape of wire, rod, and strip. As a result of these circumstances, an investigation was started to deter mine how manganin could be made on a commercial basis so that a product of uniform quality and the necessary electrical characteristics could be produced. The object was to procure an alloy with temperature coefficient of resistance not greater than T 1 X 10-5 per ° C. and a thermal e.m.f. against copper no greater than that of the imported material. It is characteristic of manganin that the temperature-resistance curve is not a straight line but has a peak, which varies in position with different samples; it is most desirable, however, to have it at a temperature of 25° C. if possible. The coefficients of manganin from all records available ranged from a large negative to a large positive value. The composition as reported by different authorities is given in Table 1. Prof. Matthew A. Hunter, of Rensselaer Polytechnic Institute, made up a number of small melts of manganin in a graphite crucible and the one that he reported as having the best coefficient gave the following analysis: Copper, 83.6 per cent.; nickel 2.5 per cent.; manganese,-13.6 per cent.; iron, 0.3 per cent. An analysis of a sample of German manganin gave the following: Copper, 82.6 per cent.; nickel, 3.8 per cent.; manganese, 12.8 per cent.; iron 0.7 per cent.

Jan 9, 1919

By A. Cochardt, D. H. Feisel

HE success of the sintered aluminum powder material (SAP)' in raising the maximum useful temperature of aluminum alloys has stimulated effort in investigating similar systems in which the metallic matrixes have higher melting points. Examples of such systems which have been studied are nickel-alumina,2, 3copper-silica,4 copper-alumina,4 titanium-cerium oxide,5 and 80/20 nickel-chromium,8 cobalt,= and molybdenum7 matrixes with various hardeners. Conventional precipitation-hardened high-temperature alloys are often thermally unstable in service. The original fine particles that are responsible for good strength properties grow in size at elevated operating temperatures, a process termed "over-aging." This growth of precipitated particles causes a gradual loss in strength properties. A previous paperb describes the factors that govern the process of overaging, and estimates the time required for overaging of a nickel-alloy matrix dispersion-hardened by various precipitates such as are found in current high-temperature alloys, and by alumina. These calculations indicate that nickel-base alloys hardened with Ni3Al, Tic, or TiN are quite unstable at 1340" F (727°F). Such alloys should overage within a few hours at that temperature. A nickel-base alloy hardened with alumina, on the other hand, should behave differently. It should not overage appreciably within a thousand years. It was further shown8 that the thermal stability of the oxide-hardened alloy is mainly due to the low solubility of oxygen in equilibrium with alumina in the nickel-base matrix. Since the oxygen solubility is small, little oxygen can diffuse, and structural changes require very long times. This paper illustrates the effects of time and temperature on the structural stability of nickel alloy matrixes hardened by dispersions of Ni3A1, Ni3Ti, Tic, and alumina, and of nickel-chromium matrixes hardened by alumina. Hardness measurements and metallography have been used as a measure of structural stability. EXPERIMENTAL PROCEDURE Using the best information from published phase diagrams,'-l4 compositions of the Ni-Al, Ni-Ti, and Ni-Ti-C alloys were determined so as to have 5 vol pct of precipitate at 1350° F(732°C), the temperature selected to illustrate the effect of time on structural stability. Table I lists the chemical compositions of these alloys. Standard laboratory melting and alloying techniques were used in preparing ingots of the F-Series of alloys. The cast ingots, 1 3/4 in. in diam, were forged to 3/8-in. diam rods.

Jan 1, 1960

By P. A. Beck, S. Kohara, M. N. Parthasarathi

IT has been shown1,3 that many observed phenomena related to annealing textures in f.c.c. metals can be adequately accounted for, at least in a qualitative way, by considering the orientation dependence of the boundary mobility, without any hypotheses concerning preferred orientation of nuclei. It was noted1 that this approach is particularly successful in the common cases of primary recrystallization in highly cold-worked polycrys-talline metals, where nuclei occur in great abundance, and that in the other extreme case, where the number of nuclei is very limited, or even only a single crystal is grown, the orientation dependence of boundary mobility has only a small effect, or none at all, on the orientations resulting from annealing. Recently Dunn described examples3-6 where observed secondary recrystallization textures apparently cannot be accounted for on the basis of oriented growth alone, but also require oriented nuclei, or at least the absence of nuclei in certain orientation ranges. In general, the great difficulty in correlating the preferred orientation of recrystallized grains with that of nuclei is inherent in the fact that nuclei are by nature very small, and that they are usually identifiable as "nuclei" only after growth, i.e., after they have already been subject to growth selectivity. An investigation was carried out by Liebmann and Lücke,' and also a very similar one by Graham and Cahn,' to obtain quantitative information on the orientation depend- ence of boundary migration rates in the recrystallization of slightly deformed aluminum single-crystal rods or plates, in which artificially nucleated recrystallized grains of predetermined orientation were grown. Liebmann and Lücke foupd maximum boundary mobility for boundaries across which the misorientation corresponded to a rotation of 40 deg around a common [Ill] axis, in accordance with earlier conclusions.9,1 Also, they confirmed that such an orientation relationship predominates among crystals growing into slightly extended single crystals from presumably random artificial nuclei. On the other hand, Graham and Cahn found no preferred orientation among crystals grown in a similar manner. It is not as yet known how these observations may be reconciled with each other. The view has been expressed in various papers5'10,21 that selective growth based on the orientation dependence of boundary mobility is not in itself sufficient to account for the formation of sharp re-crystallization textures, such as those often observed in highly deformed polycrystalline metals after annealing. The present work was undertaken to ascertain whether or not it is possible to obtain a sharp re-crystallization texture in a case where random nuclei are assuredly present in large numbers. It was previously found1' that high-purity aluminum crystals rolled 80 pct on the (110) plane in the [1T2] direction, when suitable precautions are taken, may be annealed for periods of about 1000 sec at 350°C without recrystallization. It was also found that the reluctance to recrystallize in this case is due to the scarcity of material in sufficiently deviating orientations to serve as nuclei. By using such a matrix,

Jan 1, 1959

By A. G. Guy

Thermodynamic activity rather than chemical composition is basic to the analysis of diffusion. This is the essential conclusion reached by Darken1-3 and by Birchenall and Mehl.4 If so, it is reasonable to expect that diffusion calculations should be carried out using activities. This paper will illustrate a method of employing activities in analyzing interstitial diffusion. For interstitial diffusion (of carbon in iron and probably generally) the diffusion of the solvent atoms, volume changes, and other such complexities not explicitly provided for in the usual diffusion equations cause a negligible error of the order of 1 pct. Therefore it is relatively easy to test the validity of an analysis based on activities in the instance of interstitial diffusion. The mathematical treatment of the more complex substitutional diffusion could be simplified once the adequacy of the activity method had been established for substitutional diffusion. Thus the present work has the purpose not only of providing a superior analysis of interstitial diffusion but also of indicating a possible approach to the more important question of an adequate treatment of substitutional diffusion. Development of the Diffusion Equation Although activities are convenient quantities to determine experimentally, they are derived from the more fundamental fugacities.9 Possible confusion in using activities can be avoided by basing equations involving their use on the relationship, dP = -D1d/ax dt [I] where, dP = the number of grams of solute crossing one cm2 in the time dt sec. D, = the diffusion constant for use with fugacities; it is assumed to be constant at a given temperature, and has units of secs. f = the fugacity of the solute in the solid solution; the units are those of pressure, dynes per cm2. x = the distance in cm. Eq 1 can be considered to be the basic form of the first Fick Law for one-dimensional diffusion. In order to convert Eq 1 into an equation involving activities, a choice of a standard or reference fugacity, f°, must be made: then. a = f [2] where a is the activity corresponding to the fugacity f. However, the value of a is also determined by the relation, a = a\c [3] where a is the activity coefficient and c is the concentration. For a given value of a (such as a = 1) it is evident that the units used for expressing concentration will affect the numerical value of a corresponding to a given amount of carbon dissolved in y-iron. Since weight per cent concentration is so widely used, this unit will be adopted as the standard in this paper. When the value off given by Eq 2 is substituted in Eq 1, the first Fick Law becomes, dP= -D,f°dl [4] Since D,f° is constant (at a given temperature), the second form of Fick's Law can be obtained in the usual manner, -dt D'f° dx [5] where c' is the concentration in g per cm3. In terms of weight per cent concentration, c, Eq 5 becomes, dc _ 100 d2a Tt = T /f w [6] where p is the density of the solid solution and will be assumed to be constant. In order to simplify Eq6, it is necessary to consider the standard state, f°. Standard states are chosen for convenience. There appears to be one especially convenient choice for the analysis of interstitial diffusion. If the activity coefficient, a, is set equal to unity at infinite dilution of the solute, 100 then — 100D1fl° is approximately equal P to the usual diffusion constant in dilute solutions. This is true since the activity, a, in Eq 6 can be replaced by the concentration, c, with little error in an infinitely dilute solution.* Here f1° is the standard fugacity necessary to achieve this standard state. It is proposed that a diffusion constant Da' be defined, Da1=100/pD1f1° [7] where A is the metal whose diffusion is * The second derivative of a is equal to the second derivative of c in dilute solution only if -da/dr- is. zero. Although theory does not require this condition, in the systems C in Fe, and Zn in Cu, dc is in fact found to be essentially zero.

Jan 1, 1950

By R. A. Conkling

DORSET HAGER, Tulsa, Okla. Recently we have, been doing a little work along the same lines Mr. Conkling has outlined iii his paper. I am not prepared to say that Mr. Conkling is not correct but our results do not agree with his. I think it is a question of difference in correlation and interpretation of the well records. Our cross-section of the Cushing pool does not agree with that of Mr. Conkling and we find instead of the beds thickening in the syncline, there is a tendency to thicken on top of the anticline. We took the north dome of the Cushing field, and are now trying to get all the records. It will probably be another month before we have all the data complete but our results at present do o not agree with those of Mr. Conkling at all.

Jan 4, 1917

By M. R. Geer Olds, H. F. Yancey

.I. S. Huckaba (Western Machinery Co., Spokane, Wash.)—It has been my pleasure and privilege to be able to follow this work with the H.M.S. pilot plant very closely. This has been a very thorough and painstaking piece of work and will be of great value to the dense-media operators and manufacturers. Unfortunately time was not available to make an accurate comparison between this pilot plant and the commercial plant at Bellingham Coal Mines, both plants having Wemco drum separators. Briefly I would like to point out what I consider the most interesting finding of this work. Capacity: Very good results were obtained at a feed mte of 5.2 tons per hr in a 30-in diam by 24-in. long drum separator. The maximum capacity of this drum is not known but it is something over 5.2 tons per hr for the available area of 2.08 sq ft. Medium Preparation: The importance of proper medium preparation is well demonstrated. A "tailored" or

Jan 1, 1954

By T. K. Redden

Protective coatings based on the formation of a surface coating of nickel aluminide (NiAl) were applied to the nickel-base superalloys IN 100, SEL 15, and U-700. Coated specimens were exposed to an oxidizing environment at temperatures between 1600 and 2200 F for times up to 1000 hr. The oxidation resistance and stability of the coating were evaluated by weight gain measurements, metallographic examination, and X-ray diffraction study of surface oxides and coating. The composition of the coating and diffusion zone was determined by electron microprobe traverse of samples before and after high-temperature exposure. Intermediate phases formed in the coating and diffusion zone were identified by X-ray diffraction in situ and after electrolytic extraction. The outer coating was found to consist of the inter-metallic compound, NiAl, while the diffusion zone contained MC, M23C6 or M6C carbides, and a phase in a matrix of NiAl + Nidl. Oxidation resulted in formation of an A1203 n'ch scale containing some Tz02. Depletion of aluminum during oxidation resulted in degradation of the outer coating to Ni3Al and the nickel alloy matrix. Diffusion of aluminum into the base metal was found to be slight and did not influence coating life significantly. The o formed in the diffusion zone during coating decomposed during elevated-temperature exposure to form stable carbide phases characteristic of the base metal. Diffusion zone phase changes were found to have no effect on the life of the aluminide coating in the oxidizing envzron?nent. THE oxidation resistance of many high-strength nickel-base superalloys is inadequate for extended exposure at temperatures above about 1600°F. In addition, some applications for these materials require that they be exposed to environments containing sulfur compounds and sodium salts which can cause surface attalk known as sulfidation or hot corrosion. In order to provide the necessary corrosion resistance to the high-strength alloys, protective coatings based on an aluminizing process have been developed. These processes, usually based on a pack cementation technique, result in the formation of a NiAl-rich outer coating layer either during the coating process or by a subsequent diffusion treatment. The performance of the aluminide coatings is affected by interactions between the coating layer and the base metal both during the coating process and during subsequent exposure at elevated temperatures. Knowledge of these interactions is required to guide the development of coatings capable of longer life and improved reliability. Goward et al.' recently reported the metallurgical factors which influence coating per- formance on MAR-M200. The present work is concerned with correlating the interactions and performance of coating compositions on several representative materials. EXPERIMENTAL PROCEDURES Materials. Three cast nickel-base superalloys which are used for turbine buckets in air-breathing engines were studied: IN 100, U-700, and SEL 15. Their chemical compositions are given in Table I. The alloys were vacuum-induction-melted and cast to slabs approximately 0.3 in. thick from which rectangular specimens 0.25 by 0.5 by 1 in. were machined. Coating Procedures. The machined specimens were coated by CODEP processes which were developed at the author's laboratory. These are based on pack cementation in various media to deposit either aluminum or aluminum in combination with titanium. The coating process which deposits only aluminum is designated CODEP-C, while the CODEP-D process deposits titanium in combination with aluminum. The CODEP-D process was applied only to IN 100. Both CODEP processes are applied at 1950" or 2000°F for 4 hr without need for a subsequent diffusion treatment. An outer coating about 1 mil in thickness is produced by these processes. Test Procedures. Coated specimens were exposed to static oxidation for periods ranging from 24 to 1000 hr at temperatures of 1600" to 2200°F. Terminal weight gain measurements and visual examination were used to evaluate oxidation resistance. including oxide spalling and coating failure. Both as-coated and exposed specimens of each alloy were studied by metallographic examination, electron microprobe analysis (EMA), and X-ray diffraction analysis either of the exposed surfaces or of phases extracted from the coating and diffusion zone. RESULTS As-Coated Condition. The microstructures of as-coated conditions were generally similar, irrespective of base materials or the particular coating process. They are typified by IN 100 coated by CODEP-D as shown in Fig. 1. The predominately single-phase outer layer, area A, Fig. 1, was identified by X-ray diffraction as the intermetallic compound NiA1. The NiAl zone extended inward to the original base metal interface. The diffusion zone, area B, Fig. 1, included carbide phases, a lamellar phase oriented perpendicular to the base metal surface, and a matrix phase consisting of a mixture of NiAl and Ni3Al. The phases in the diffusion zone were electrolytically extracted using a 10 pct HCl in methanol solution at approximately 1.3 amp per sq cm. The extracted phases were found to be M6C, MC, or M=C6 carbides and o as shown in Table I1 for each of the alloys. The d spacings from a typical diffraction pattern are

Jan 1, 1969

By G. R. Rubly, H. J. Steele

LOCATION AND HISTORY THE San Manuel property is in townships 8S and 9S, range 16E, Gila and Salt River Base and Meridan, State of Arizona. This area is in the Old Hat mining district, southern Pinal County, and is about 3;2 miles southwest of the town of Mammoth on the San Pedro River and one mile south of the Mammoth mine at Tiger, Arizona. The property consists of over 150 contiguous lode claims. The Old Hat district was prospected prior to the Civil War, but there was little or no production until 1881.1 The chief producers have been the Mammoth and Mohawk mines, now consolidated and operating as the St. Anthony Mining and Development Co., Ltd. Production to 1936 was $5,200,000, of which 83 pet was gold.2 Since 1940 the production has been chiefly lead and zinc, and some molybdenum and vanadium. There are a few small properties in the vicinity that have produced very minor tonnages of copper ore. In the San Manuel group there are claims which have been held continuously from 1906 to the present time, and at least two churn-drill holes were put down on or near the outcrop in 1917. No logs for these holes are available, but it is assumed that the grade of copper encountered was not sufficient to encourage further exploration. A small amount of ore has been shipped from open cuts on the San Manuel outcrop area, but there is no record of the tonnage or grade. It is estimated that not more than 5o tons were mined. These cuts, plus a few shallow shafts and some short adits indicate limited and unenthusiastic prospecting at San Manuel. In 1942, through the efforts of James M. Douglas, R. B. Giffin, Victor Erickson, and Henry W. Nichols, owners of the San Manuel group, the Reconstruction Finance Corporation and War Production Board authorized the United States Geological Survey to investigate the property, and by their recommendation, the United States Bureau of Mines was authorized to put down a limited number of churn-drill holes. The Bureau of Mines carried on drilling from November 1943 to February 1945. Seventeen holes were drilled, varying from 305 to 1990 ft in depth. The property was brought to the attention of Magma Copper Co. in June I944 and an option agreement was made with the owners. Subsequently, a group of claims lying north of the original group and held by the Apex Lead Vanadium Mining Corp., and a group to the east held by the Quarelli family, were optioned. A drilling program was laid out to conform to the Bureau of Mines pattern, and drilling started in December 1944. San Manuel Copper Corp. was incorporated September 1945, and has carried on the exploration program to the present time. GEOLOGY General The mineralized outcrop, chief copper mineral of which is chrysocolla, is a tri-

Jan 1, 1947

By F. C. Greene

Development work in western Missouri was continuous during 1933, owing to the shallow depths at which production is obtained and the low operating costs. Unfortunately, no statistics covering the total production of oil and gas during the year are available. No new oil-producing pools were opened in 1933, but the Knoche area in 1.46 N., R.33 W., Cass County, was extended. There are probably less than 100 producing oil wells, all in Cass and Jackson counties, with a combined production of possibly around 150 bbl. daily. Several new gas areas were developed and there were several extensions of old areas, in 1933. Production was extended north by an entirely new pool—the Hammond pool, north of Plattsburg in Clinton Co. (sec. 18, T.55 N., R.31 W., and sec. 13, T.55 N., R.32 W.) where 13 wells were completed, the largest producing 2,332,000 cubic feet. In the Bartle and Marshall pool in secs. 3-4-9-10, T.47 N., R.33 W., Jackson County, four wells opened a new area. The largest well was 1,000,000 cubic feet. There were some small extensions near Independence, Jackson County. Two wells of about 300,000 cu. ft. were completed at a depth of 700 ft. in Kansas City and in a deeper sand than is usually productive. The Shaler area, in secs. 27-34, T.44 N., R.33 W. in Cass County, was extended with several wells, the largest of which was 300,000 cubic feet. The production in the pools mentioned is obtained chiefly from the Henrietta and Cherokee formations of the Pennsylvanian age.

Jan 1, 1934

By M. Metzger, L. E. Hendrickson

Grain boundary attack in 16 pct HCl was found to be substantially the same at low penetrations in zone-refined aluminum (individual impurities 0.1 at. ppm), superior electrolytically refined aluminum (51 at. ppm), and aluminum with various impurities at much higher levels. It was concluded that impurity atom segregation affecting corrosion would have been detected and that the corrosion susceptibility did not originate in this segregation but in the structure of the boundary. It was pointed out that the significance of most previous studies in this system had been obscured by an unrecognized autocatalytic copper reaction. Although general corrosion rate was also impurity-insensitive , there was shallow pitting attributed to iron seg-regation and a hillocked surface texture associated with copper; these were interpreted as due to cathodic damage affecting- cathode distribution. THE grain boundary corrosion suffered by high-purity aluminum in hydrochloric acid has been the object of some interest (the earlier work is summarized in Ref. 1). The central metallurgical question here is whether the corrosion susceptibility of a boundary originates in its structure or in impurity atom segregation. An attempt to study this question revealed large catalytic effects associated with small quantities of the copper impurity in the aluminum, 220 ppm, or in the corrodent, and these magnified the preferential boundary attack and obscured the intrinsic susceptibility question.' After the catalytic effects had been examined,"' test conditions could be designed to avoid them and methods developed for studying the shallow boundary penetrations prevailing when they were absent.= It then became possible to determine whether intrinsic boundary corrosion in aluminum involves impurity segregation. The older work provided no firm information on grain boundary segregation of specific solutes influencing corrosion although several studies suggested iron segregates.4,5 perryman4 found in 10 pct HC1 that the slowly developing (microns per month) grain boundary grooves were deeper in material of higher iron content (range 10 to 550 ppm, with 5 to 80 pprn Cu) but he did not measure the depths of general corrosion, which were probably several times greater, and his reference surfaces may have varied more than did the groove depths. Metzger and Intrater's results for 20 pct HC~,' which yielded higher time-average rates (mm per month) and deeper penetrations, suggested that boundary segregation of iron (range 4 to 230 ppm, with 22 pprn Cu) decreased the penetration rate. However. in the stronger acid the autocatalytic l.E. HENDRICKSON, Student Member AIME ,and M. METZGER, Member AIME, are Research Assistant and Professor of Physical Metallurgy, respectively, Department of Mining, Metallurgy and Petroleum Engineering, University of Illinois, Urbana, Ill. Manuscript submitted March 11, 1968. IMD effect of the copper impurity is greater1,2 and it is now evident that their corrosion rates had been much magnified by this effect and did not provide a proper basis for the analysis of segregation. In exploratory studies of other solutes (made under the same conditions), 1000 ppm additions of Mg, Mn, or Si or 100 ppm Ca were without effect.1 Montariol6 noted that boundary attack in 22 pct HC1 persisted after zone refining although with fewer deep fissures (ranges 0.06 to 4 ppm Cu, 4 to 23 ppm Fe). Autocatalytic effects may have influenced these results also and those of Perryman.4 The present objective was, as a first step, to see whether quantitative tests designed to exclude autocatalytic influences would indicate the existence of low-level impurity effects on intrinsic boundary corrosion. Comparison of electrolytically refined with zone-refined aluminum of lower copper and iron contents revealed no differences in boundary corrosion, but certain impurity-sensitive differences in general corrosion morphology were noted and investigated further at higher impurity levels. I) EXPERIMENTAL PROCEDURE A) Material. A selection from commercially available material was made with the cooperation of several producers. An electrolytically refined lot (III-A, 1 ppm Cu, 2.4 ppm Fe) studied previously3 provided a starting point. Since material of substantially higher copper content could not be used if the autocatalytic corrosion reaction were to be avoided,2,3 a lot (III-B) of about the same purity was added as a check, two zone-refined lots (I-A and I-B) with copper and iron an order of magnitude lower were selected for comparison, and an intermediate lot (11) was included. Analytical data are given in Table I. For copper in I-B and iron in I-A and I-B, the actual concentration is thought to be near the limit given, i.e., about 0.1 ppm. For titanium, vanadium, and chromium in III-B, the actual amounts are thought to be, like those in III-A, substantially lower than in the zone-refined lots (these elements concentrate in the solid on freezing). Data are given later for some additional lots surveved. B) Specimen Preparation and Procedure. one by 3 cm blanks with a notched stem were cut from 1-mm cold-rolled sheet, annealed 24 hr in air at 650°C, and quenched in an air stream (42°C per sec initial cooling rate, 100 sec to cool to 100°C). The high annealing temperature maximized diffusivities and approach to equilibrium impurity distributions. A water quench, in principle more efficient in preserving the distribution established, was undesirable because the boundaries were almost plane and they tended to shear and migrate during the quench and thus to be separated from any existing impurity atmosphere. Test procedures, previously described,3 involved electropolish-ing, etching 2 min in 10 pct HF at 24.0°C, and expos-

Jan 1, 1969

By W. T. Hicks

The oxidation of CbO was studied by a gravimetric technique from 400° to 1200°C in oxygen. In this temperature range the oxidatiotz is characterized by an irlductive period of low oxidation rate, which becomes shorter as the temperature increases, followed by a rapid parabolic oxidation. The oxidation of CbO cannot be rate controlling in the oxidation of Cb metal in the temperature range, 800° to 1200°C. A thin optically inactive layer has been observed between the metal and Cb2O5 layer of Cb oxidized at 700°C or higher temperatures. Figs. 1(a) and 1(b) show the edge of a sample of Cb reacted to 50 pct of complete oxidation at 800°C. Fig. l(a) taken under bright field illumination shows a layer of oxide adhering to the unoxidized metal core. Fig l(b) taken under polarized light shows that this oxide layer is

Jan 1, 1962